DE3410616A1 - PHOTOGRAPHIC, LIGHT-SENSITIVE SILVER HALOGENIDE MATERIAL - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material containing a compound capable of imagewise a visualizing agent or a development accelerator to release, the sensitivity and the gradation is increased and the development is accelerated will. In particular, the present invention relates to a color photographic, light-sensitive silver halide material, in which the graininess is improved although the material has high sensitivity .

There has recently been a great deal of effort to increase the speed of silver halide photographic light-sensitive materials, particularly those used for photographic purposes, as is typically demonstrated by ISO 400 films and the like. To increase the sensitivity, a variety of techniques have been investigated, including for example the use of large silver halide grains of couplers having higher activities, the accelerated development and the like. However, the limit of increasing sensitivity seems to have been reached based on the use of large silver halide grains as reported by GC Farnell and JB Chanter in Journal of Photographic Science, Volume 9, page 75 (1961). Accordingly, this technique is not expected to make much contribution in the future.

The use of large sized silver halide grains has furthermore, numerous disadvantages such as deterioration in graininess, increase in the thickness of the emulsion layer and deterioration in shelf life. Farther is the increase in sensitivity by using couplers with higher activities or accelerated development disadvantageous in that these methods are not only accompanied by a noticeable deterioration in graininess are, but also not a major contribution to

BAD OBSQiNAL _G0P Y

Contribute sensitivity. In terms of acceleration numerous development accelerators, including hydrazine compounds, in a silver halide emulsion layer or a developing solution therefor, mainly for photographic, light-sensitive black-and-white materials, incorporated. In most cases, however, the familiarization of Development accelerators in an emulsion layer or a developing solution associated with disadvantages, such as an increase in fog and a deterioration in graininess, making them unsuitable for practical use are .

Furthermore, couplers which imagewise release development accelerators or fogging agents have also been proposed. For example, couplers that release thiocyanic acid ions which accelerate physical solution development are described in U.S. Patents 3,214,377 and 3,253,924 or JA-OS 17437/76. Likewise, couplers that release hydroquinone or aminophenol developing agents are described in JA-OS I3836 / 82. However, the development accelerating or fogging function of these releasable groups is poor, so that the effects obtained are very poor even when couplers releasing these groups are used in a large amount. In order to overcome these problems, couplers that release acylhydrazines as described in US Pat . No. H 390 "G18 and couplers that release thiocarbonyl compounds as described in JA-OS 1615 Vj / 82 (corresponding correspondence) have been used US patent application, Serial No. 532 631 and DE-OS 3 333 355-6), a high sensitivity being achieved with these couplers.

However, it has been found that these couplers have the disadvantage have that color mixing occurs and the color reproducibility t is reduced because the releasable groups are in other layers facing light one are sensitive to different spectral ranges, diffuse, to cause a development acceleration

BATH ORIGINAL

or veil due to their high diffusivity form when this in a certain photosensitive Layer that is sensitive to light of a specific spectral range can be incorporated. as well it has been found that these couplers suffer from the disadvantage of graininess as compared to cases where these Couplers cannot be used to increase sensitivity, as the releasable groups deteriorate in the layer to which they are to be added or in a layer that opposes light of the same spectral range is sensitive, diffuse unhindered, under Causing development acceleration or fogging even if not in layers that sensitive to light from a different area

15 are diffuse.

On the other hand, other methods of increasing sensitivity have been proposed based on studies of the layer structure of photographic light-sensitive materials. For example, there is a method for achieving high sensitivity in an emulsion layer in which a layer containing fine reflective particles is provided below the emulsion layer in order to utilize the light scattering function due to these fine particles, as described in Research Disclosure , Volume 134, page 47 , No. 13452 (1975). This procedure actually increases the sensitivity. However, the increase in sensitivity in this method is at most two times due to the light scattering effect only, and the method has a problem in practical use that the graininess as well as the increase in the sensitivity is markedly deteriorated.

It is therefore an object of the present invention to provide a silver halide photographic light-sensitive material with high sensitivity and improved graininess to accomplish.

PAD ORIGINAL

Ai ₀

Another object of the invention is to provide a silver halide photographic light-sensitive material having good color reproducibility.

Further objects of the invention are made based on the following Description and examples can be seen.

These goals are achieved according to the invention with a A silver halide photographic light-sensitive material comprising a support having thereon at least two located, light-sensitive silver halide emulsion layers, which are sensitive to light of essentially the same spectral range and one relative light-insensitive layer containing silver halide, zinc oxide or titanium oxide between the two light-sensitive Silver halide emulsion layers are arranged, wherein at least one of the two photosensitive Silver halide emulsion layers contain a compound of the following general formula (I):

A-B (I)

where mean:

/ - a hest of a compound necessary for coupling with the oxidation product an aromatic primary amine developer by the removal of a hydrogen atom from the active position of the compound is capable and

P is a group that is released upon coupling and, in a development solution, has a concealment function

b ".w. Sch 1 ei obtained.

As mentioned earlier, when the compound represented by the general formula (1) is converted into a silver halide emulsion J nnr.iohlicht is incorporated, the graininess in the

Compared to the case in which this connection is not incorporated, is deteriorated, color mixing occurs and color reproducibility is lowered,

Air

/ ζ

although the sensitivity increases. To a deterioration To prevent graininess, it is very effective to use a relatively light-insensitive emulsion of a layer, containing the compound of the general formula (I). However, this procedure results in most of them Cases in a suppression of the increase in sensitivity, although a small increase in sensitivity is observed will. Furthermore, it is very effective to have a relatively light-insensitive emulsion layer between emulsion layers , which are sensitive to light of a different spectral range from each other, to provide improve color reproducibility, but in most cases there will be a significant increase in sensitivity, as achieved according to the invention, not obtained. Surprisingly It has now been shown that according to the present invention not only increases the sensitivity, but also the robustness is improved. These effects are particularly shown in the examples below.

The inventive compound of the general Formula (1) is described in detail below.

In the general formula (I), the coupler radical represented by A is in particular a radical which is different from a Blue-green coupler, magenta coupler, yellow coupler, or a non-color forming coupler. The one represented by B, A group exercising a veil function is in particular a group containing a partial structure of a reducing compound, such as a hydrazine, hydrazine, hydrazone, enamine, polyamine, hydroquinone, aminophenol, Phenylenediamine, acetylene, aldehyde and the like or a compound capable of forming silver sulfide, for example a thiocarbonyl compound, as typically represented by a thiourea, thiocarbamate, Dithiocarbaroate, rhodanine, thiohydantoin and the like.

Of the compounds represented by the general formula (I), compounds represented by the following general formula are preferred

_vrt j ORIGINAL

(II) inserted:

A- (TIME) -FA

^η (ID

where mean:

A has the meaning given for A with respect to the general formula (I);

TIME is a timing group or control group that takes part in the Coupling is released and then FA is released in a developer solution;

η 0 or 1; and

FA a group that can be released from A on coupling when η is 0 or released from TIME when η is 1 and has the ability to be adsorbed on silver halide particles and thereafter exerts a fogging effect on silver halide.

One group capable of subsequently exerting a fogging effect on silver halide is one Group (compound) which forms a measurable fog when a photographic light-sensitive material of Is subjected to development processing in the presence of the compound.

Examples of FA include groups of the formula AD- (L) -X-J- and a group having the functions of or the structures of both AD and X. In the above formula, denotes AD, a group that can be adsorbed onto silver halide particles; L represents a divalent linking group; X represents a reducing group or a group capable of forming silver sulfide upon development;

ü 5 m has the meaning of 0 or 1.

Is FA ej nc represented by the formula AD- (L) -X-I-

L m J

Group, so can dipr; e group on TIME (or A) on a

BATH

1 suitable position hereof be bound. Naturally

is a group that is also the functioners! of both AD and X are also preferred.

Examples of coupler residues represented by A include Residues of cyan couplers such as phenol and naphthol couplers; Solids of purple couplers such as 5-pyrazolone couplers, Pyrazole benzimidazole coupler, pyrazole triazole coupler, Cyanoacetyl Coumarone Coupler, Open Chain Acylacetonitrile couplers or indazolone couplers; Residues of yellow couplers such as benzoylacetanilide couplers, pivaloyiacetanilide couplers or malondianilide couplers; and residues of non-color forming couplers such as open chain or cyclic, active methylene compounds (for example indanones, cyclopentanones, diesters of malonic acid, Imidazolinones, oxazolinones or thiazolons).

The coupler residues represented by A, which are preferred according to the invention are used include those represented by the following general formulas (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) or (XI) residues shown:

r "

25 ^Μ -Ν ^ ϋ

in which mean

R- an acylamide, aniline or ureide group; 30th

and

Rp is a phenyl group represented by one or more Substituents selected from the group consisting of halogen atom, alkyl group, alkoxy group and cyano group, below can be;

• r * *

(IV)

(V)

con:

5 (VI)

where mean:

R ^ a halogenator, an acylamide group or aliphati see group;

Rj, and PL · each represent an aliphatic, aromatic or heterocyclic group, where one of R ₂ and R _{P can represent} a hydrogen atom;

a is an integer from 1 to 4; b 0 or an integer from 1 to 3; • c 0 or an integer from 1 to 5;

⁶ ! I!

⁰ ° ^R 7

CVII)

■ '-NHCCHCNH-

«I.

^R 7 ^R 7 (VIII)

where mean:

Rg is a tertiary alkyl group or an aromatic group Group;

Ry hydrogen atom, halogen atom or an alkoxy group;

and

Rg an acylamide group, an aliphatic ^ group, a Alkoxycarbonyl, sulfamoyl, carbamoyl, alkoxy group, a halogen atom or a sulfonamide group; 25th

^R 9

where mean:

Rg is an aliphatic group, an alkoxy, mercapto, Alkylthio, acylamide, alkoxycarbonyl, sulfonamide, Carbamoyl, sulfareoyl, alkoxysulfonyl, aryloxysulfonyl, Acyl, diacylamino, alkylsulfonyl or arylsulfonyl group;

and

R _{1n represents} a hydrogen atom, halogen atom, an alkoxy, acyl, nitro, alkylsulfonyl or arylsulfonyl group;

where that represented by the general formula (IX) Indanone group may exist in the form of an enol ester thereof;

11.

where mean:

R _{11 is} an aliphatic or aromatic group;

and

V is an oxygen, sulfur or nitrogen atom;

^R 12 " ^C " ^R 13

H (XI)

where mean:

R.ρ and R ₁ -. in each case a group selected from the group of the following formulas

-N

> r 23

T ^{Rl4 /}

-CNH

!! ²

-R

-cn;

14th

15th

Il ο

ii ¹⁴
O -SR,. ,
i! ^14th
O O
! j 0
Il 'J
-SNH. ,,
i! ² "O ii
0

\ L4

-CN,

-CKO,

U4

-NO

NO.

or

where mean:

^{35 R} 14 ' ^R 15 ^{and R} - _S 5 each represent a hydrogen atom, an aliphatic, aromatic or heterocyclic group;

and

copy

2'Ψ

W die to form a 5-r or 6-membered ring together with the nitrogen atom, necessary, non-metallic Atoms or where FLp and R.-, in correlation together with the necessary, non-metallic atoms

^{5 can form} a 5- or 6-membered ring.

The timing group represented by TIME in the general formula (II) includes a group represented by the Coupling of A is released and subsequently releases FA due to an intramolecular rearrangement reaction, as described in U.S. Patent 4,248,962 or JA-OS 56837/82, a group that releases FA by means of electron transfer via a conjugate system, as described in US Pat GB-PS 2 072 363 A or JA-OS 154234/82 and 188035/82,

or a group of a coupling component that contributes to the free-15

Setting of FA on coupling with the oxidation product an aromatic, primary amine developer, as described in JA-OS 111536/82. These reactions can occur in one stage or in several stages.

20 Γ Ί

If FA is one represented by the formula AD- (L) -X-4-

L m _j

Group, AD can be attached directly to the carbon atoms at the coupling position, or L or X can be attached to the Carbon atom attached to the coupling position,

as long as L or X are released at the coupling 25

can. Furthermore, the so-called 2-equivalent releasable group between the carbon atom on the Coupling position and AD are available. Examples of such 2-equivalent releasable groups include an alkoxy group (e.g. a methoxy group), an aryloxy group (e.g. a phenoxy group), an alkylthio group (e.g. an ethylthio group), an arylthio group (e.g. a phenylthio group), a heterocyclic oxy group (for example, a tetra: '- · 1 y 1 cxy group), a heterocyclic thio group (e.g. pyridylthio group), a heterocyclic Group (for example a hydantoiny1 group, pyrazolyl group, Triazo] y1 group or benzotriazolyl group).

410616

you can continue to use those in the British patent application; 2 Oll 391 A groups described as FA.

Examples of shown by AD, for absorption αι.! Γ Silver halide capable groups include a group derived from a nitrogen-containing heterocyclic Ring with a dissociable hydrogen atom ; "for example pyrrole, imidazo !, pyrazoi, triazoi, tetrazo !, 3enzimidazoi, 3enzpyrazole, benzotriazole, uracil, Tetraazaindene, imidasotetrazole, pyrazolotriazole, pentaazaindene ) a heterocyclic ring,

containing at least one nitrogen and at least one another heteroatom (for example an oxygen, sulfur or selenium atom) in its ring (for example

15 Gxazoi, Thiazol, Thiazolin, Thiazolidin, Thiadiazol,

Senzothiazole, benzoxazole), a heterocyclic ring with a mercapto group (for example 2-mercaptobenzothiazole, 2-mercaptopyrimidine, 2-mercaptobenzoxazole or 1-phenyl-S-mercaptotetrazole), a quaternary salt (for example a quaternary salt of a tertiary amine, pyridine, quinoline, benzthiazole, benzimidazole or benzoxazole), a thiophenol, alkylthiol (e.g.

Cysteine), a compound with a partial structure of S.

>. I.

M-C- (for example a thiourea, dithiocarbamate, Thioarnide, rhodanine, thiazolidinthione, thiohydantione or thiobarbituric acid).

The divalent linking group represented by L in FA may be a group selected from commonly used divalent groups including, for example, an alkylene group, alkenylene group, phenylene group, naphthylene group, -0-, -S-, - SO-, -SOp-, -N = U-, a carbonyl group, amide group, thioamide group, sulfonamide group, ureide group, thioureid group or heterocyclic group.

Examples of groups represented by X include one

Group that is derived from a reducing compound (for example a hydrazine, hadrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine, 1-Phenyi-3-pyrazolidinone, enamine, aldehyde, polyarain, Acetylene, aminoborane, quaternary salt such as tetrazolium salt or Ethyienbispyridiniurasalz or a carbamic acid) or a compound capable of forming silver sulfide during development (e.g. a

S 10 connection with a partial structure " ^V _N _ _C _, such as

a thiourea, thioamide, dithiocarbamate, rhodanine, Thiohydantoin or thiazolidinthione). Among these, capable of forming silver sulfide during development, Groups represented by · X can be specific groups

are adsorbed on silver halide particles themselves,

so that these can also act as the adsorbing group represented by AD.

FA can be at TIME or A at the adsorbing site for

Silver halide particles (for example, a nitrogen atom of benzotriazole or a sulfur atom of 1-phenyl-5-mercaptotetrazole) be bound, but is not limited to this. In the latter case, it is preferred that a Hydrogen atom is bound to the adsorbing site

or that the adsorbing site with one in one

Developer solution hydrolyzable group (for example an acetyl, benzoyl or methanesulfonyl group) or a group that can be released in a developer solution (for example a 2-cyanoethyl or 2-methanesulfonylethyl group) is blocked.

Specific examples of AD that can be used are shown below.

ORIGINAL BATHROOM

N.

N-N

N-N

-S

-S

N-N

-S

N - N

N H

Ν - N

CH

V Si it * W t> *

a »β

-s -λ:

\. U

N /

N N N

-S

■ · <

N H

■ CH

bath

COPT

CH

CH

-NHCNH-

-NHCS-

H"

-CH ₂ CNH-

Specific examples of L that can be used are listed below:

BATH ORIGINAL

10

-OCH ₂ CH ₂ -,

10

-OH

-CONH

0 ii OCNH

i!
-SCNH

-OCO

-NHCNH

35 -NHCNH

II -CH _? CNH

Ii -CH ₂ CH ₂ CNH

-SCH ₂ C

-COO

CONH

CONH- ^ \),

SO

NH-V W

'II NHCNH

OCH

CONH

Ii NHCNH

/ -OCH ₀ CONH

COO

CONH

COO

COO

C.

CONH

Copy

IAD ORIGINAL

-SCHACH, CONH-

-SCH ο C ¹ H "COO

-SO ₇ CH ₉ CONH

2 ^Wi 2

-SO ₂ CH ₂ CH ₂ C

-NH

CONH

-O

C ONH - // \

CONHCH ₂ - // \ N =. /

BATH ORIGINAL

% Ψ

1 Specific examples of X that can be used are given below:

NHNHCHO, - NHNHCOCH 3, NHNHSO ₂ CH ₃ , -NHNHCOCF ₃ N - NHCH

COOC ₂ H ₅

-CONHNH

-CONHNH

OCH

C = N-NH

-CH

- C 0 N HN HCH, - C 0 N HNH

. -C-C-H

-CHO

S.
i!
-NHCNHCH

Il CNH

- S - C N H C H

Copy

■ 'tU

33-

N H

Specific examples of FA in the general formula (II), which can be used are listed below:

CONH

CH ₂ CONH

NHNHCHO

NHNHCHO

-s

SCH ₉ CONH

NHNHCHO

N N

-S

SCH ₉ CONHNH

CH

N N

SCH ₂ CN-NH I CH,

S ■ <■

CU., CHO

CONHXHCH-,

Copy

BATH ORIGINAL

CONH

NHNHCHO

SO ₉ NH

NHXHCHO

BrO

CH ₂ C = CH

Br

CH ₉ CH ₉ C = N-NH

CH

COPY

.. ^: '-: 34Ί0616

-OCH ₇ CH ₉ N

2 ^ν - ^1Ί 2

CH

CH

N - N

in

NHCO

N.

N - N

I I:

CH ₂ CH ₀ NHCCH. copy '

BAD ORIQlMAk

1 Specific examples of preliminary bindings which can be used according to the invention of the general formula (J) are given below:

^) ₃ OC ₁₂ H ₂₅ -H

O C H, C O NK - </ \ / - N H N H C i I C)

(2)

OH

CONHC _1fi H

-n

OCH ₂ CH ₂ SCh ₂ CONH

NHNHCHO

13}

CONHC ₁₆ H ₃₃

.N

OCH ₀ NN \ /

CONH

NHNHCHO

UMSGiNAL

ae

4)

NHNHCOCH.

N HCOCHO

C ₂ H ₅

(5)

C £

NH

C ₃₃ H ₂₇ CONH N

SCh ₂ CONHNH - ^ /

IyA

NHNHCHO

(7) CH ₃ O

COCHCONH

Currently

CONH

COOC ₁₂ H ₂

-NHMlSn ₂ CH ₃

BAD ORIGINAL COPY

(8th)

CH ₃ CH, -C-COCHCCNH

NHCO (CH ₉ )

2 '3

CH-

N '

₅ H, it

-NHNHCOCF.

(9)

QI ₃ CH .. -C-COCHCONH

, N

COOC ₁₂ H ₂₅

CM

NHNHCHO

copy

r ¥ -3

do)

CONHC ₁₅ H ₃₃

S! I OCH ₀ CH ₉ NHCN

(H)

OH

CONHC ₁₆ H _a

3 C ₀ H,

OCH,. CH. NHCN

OH

CONHC ₁₆ H ₃₃

OCH, CH, .NHCNH

(13)

CONHC ₁₆ H ₃₃

O S

Il NHCNHCH

CH ₃ υ - </

/ W

COCHCOXH

Ct '

• Ν

COOC ₁₂ H ₂₅

ίο

20th

30th

in C-:

35 SAP ORIGINAL

ο:

to cn

cn

f lfi)

CU,

π-Γ, ₂ II _{2 5} 0 HOC IIOCO

NHCOCHCONH

CH ₃
I.
COOCnCOOC ₁ 5 H ₂₅ -η

NIINHCIIO

t ie »*

10

15th

(17)

CH, 0

2 5 ~ ^π

SCH ₉ CONH

NHNHCHO

CH,

COCHCO

NHCXH

NHNHCI-IO

BATH ORIGINAL. j

(19)

CH, O - (/ V-COCHCONH

COOC ₁₂ H ₂

(20)

SCH ₂ CONHNH - ^ / V "CH ₃

CH ₃ O

\) - C0CHC0NH ■ zJ \

COOCHCOOC, ₂ H _{2 5} -n

CH ₃

\ - </ \ V-CON H

NHXHCHO

"1 ·} w ORIGINAL

yC Ή *

(21)

CH

CHoO

COOCHCOOC ₁₂ H ₂₅ -n

NHNHCHO

('22)

NHCO (CH ₉ )

2 - 2

CH ₃ - ^ c-COCHCONH

CH,

~ ^ι

C ₅ H ₁₁ -I

CONH-

NHNHC0CH-.

COOC _{1 2} Η _{2 5} -η

NHNHCHO

15th

20th

25th 30th 35

copy

ORIGINAL ι

left

(25

10

15th

OH

CONH

CONH

20 25 30 3 5

(26}

OH

CONH

^l 2 9

NO.,

CONH- ^ y y-NHNHCHO BAD

(27)

COOC ₁₂ η ₂₅ -η

CH ₃ O

SCH ₂ C = N-NH

! CH.

(28)

CH ₃ O

COCHCONH-

N N-CH ₂ CH ₂ CHO

a

(29)

(30)

CONHC ₁₆ H

3

CONHNHCH

OH

CONHC _{1 6} H _{3 3} -n

i!

OCH _o Cl] ο NHCNlW / V-NHNHCHO

(31)

CONHC

-π

(32)

OCH.CH.N

copy

BATH ORIGINAL

SC

CONHC ₁₆ H ,, - π

OCH ₉ CH ₉ N

2 ^ ¹¹ 2

NH

(34)

OH

: ONH-V \

OC ₁₄ H ₂₉ -H

NHCU

Sill

410 616

10

ⁿ ~ ^C l8 ^H 3 7 ^OCOCHCOOC 18 ^Η 37 ~ ^π

CONH

NHNHCHO

15th 20th 25th

(3 6)

CH ₃ 0 - (/ X) -COCHCONH-

CH ₃
COOCHCaOC ₁₂ H ₂₅ -π

Λ /

COMI

STINHCf 10

BAD ORIGINAL ^C0PY

CH ₃ I CH ^ -C-COCHCONH

CH

^COOC i ₂ H ₂₅ -n

N = N

CONH

NHNHCHO

(38)

CH ₃ O

COCHCONH

COOC ₁₂ H ₂₅ -n

N ^:

N /

\ COO

CONH

bath

NHXHCHO

S ⁰ S

(39)

CONH

COOCH ₉ CONH

JVHNHCHO

The compounds used according to the invention of the general Formula (I) can be given by the in JA-OS 138 636/82. U.S. Patent 4,390,618 and JA-PS 161515/82 (corresponding to the U.S. Patent application, serial no. 532 631 and DE-OS 3 333 355.6).

Two or more compounds of the general formula (I) can be used simultaneously in the present invention, if desired.

According to the invention, the compound of the general formula (I) can be used together with a DIR compound which has a diffusible, releasable group releases, as in JA-OS 1519 ^ / 82 or a DIR connection with a time control function, as described in JA-OS 15 ^ 23 ^ / 82 and 188035/82 or U.S. Patent 4,298,962, may be used, sometimes obtaining preferred results in terms of graininess, sharpness and color reproducibility will.

Likewise, in order to further improve the granularity, it is preferred in the present invention in some cases to use the compound represented by the general formula (1) together with a coupler

to use, which forms a diffusible dye, as described in JA-OS 82837/82.

Furthermore, it is in terms of improving graininess sometimes preferred according to the invention, the compound of the general formula (I) together with a hydroquinone or a compound capable of scavenging the oxidation product of a developer, as in U.S. Patents 4 252 893 or 3 ^ 57 079 to use. 10

According to the invention, the amount of the compound of the general formula (I) used is not more than 1 mol, preferably 10 "mol to 0.2 mol, in particular preferably

_7

adds 10 'moles to 0.01 moles per mole of silver in the compound containing layer. In particular, the amount of the compound of the general formula (II) is not more than 0.1 mole, preferably 10 "mole to 0.05 mole,

-7 -2

particularly preferably 10 moles to 10 moles per mole

Silver in the layer containing the compound. 20th

The relatively light-insensitive layer used in the present invention may be completely light-insensitive Layer containing only zinc oxide or titanium oxide or containing an essentially light-insensitive layer Extremely low sensitivity silver halide.

A preferred particle size for the zinc oxide or titanium oxide as Π ndung5; as used in the relatively lichtunempf indliehen layer is about 0.05 pm to 0.8 .mu.m and more particularly from 0.05 to 0.5.

A relatively insensitive silver halide emulsion. ^r : chicnt .; containing silver halide particles having substantially no sensitivity is preferred for the relatively light-insensitive layer in the present invention.

f'ie erf i ndungsgemäß used, relatively lichtunempfind-

BATH ORIGINAL

The silver halide emulsion layer is described below described in detail.

The sensitivity of the relatively insensitive to light Silver halide emulsion layer according to the invention should be at least 0.5 and is preferably around at least 1.0, expressed in log units, less than that of a layer with a lower sensitivity of the adjacent, light-sensitive silver halide emulsion layers.

Any pure silver chloride, pure silver bromide, pure Silver iodide, silver chlorobromide, silver iodobromide and According to the invention, silver chloroiodobromide can in the relatively light-insensitive silver halide emulsion are present.

Silver halides containing 60 mol% or more silver bromide, 30 mol% or less silver chloride and 40 mol% or less silver iodide are preferred. The particle size of silver halide is not critical, but is preferably about 0.6 µm or less, and most preferably preferably 0.04 to 0.4 μm. In particular, the particle size is 0.08 to 0.25 µm when the relatively light-insensitive silver halide emulsion layer is between arranged blue-sensitive silver halide emulsion layers is 0.1 to 0.3 µm when the relatively light-insensitive silver halide emulsion layer is between green-sensitive silver halide emulsion layers is arranged and 0.1 to 0.4 ym if the relative light-insensitive silver halide emulsion layer between red-sensitive silver halide emulsion layers is arranged. Although used according to the invention, relatively light-insensitive silver halide emulsion have a relatively broad particle size distribution can, a narrow particle size distribution is preferred. In particular is a silver halide emulsion preferably in which more than 90% by weight or number of the total silver halide particles within

of the size range of + 40% of the mean particle

size, preferred.

The amount of coated silver for the relatively light-insensitive silver halide emulsion layer is from about 0.03 to about 5 g / m ² , preferably from 0.05 to 1 g / m ² . Any hydrophilic polymer can be used as a binder in the relatively light-insensitive emulsion layer. Gelatin is particularly preferred. The amount of the binder is preferably not more than 250 g per mole of silver halide.

The relatively light-insensitive one used according to the invention Silver halide emulsion can be prepared using known methods. That is, the Emulsion can be prepared in any suitable manner, for example by an acidic process, neutral Process or ammonia process. Likewise, there can be a soluble silver salt and a soluble halide in each be implemented in a suitable manner, for example using a single-jet method, double-jet method or a combination thereof. One type of double jet process is a process in which the pAg in the liquid phase in which the silver halide is formed is maintained at a constant value (the so-called controlled double jet process).

According to this method, a silver halide emulsion having a narrow particle size distribution can be obtained, so that this method is preferred for preparing the relatively light-insensitive silver halide emulsion used in the present invention. The relatively lichtunempfjndlichen silver halide particles may have a regular Krjstall form such as a cubic, octahedral, or tetradecahedral form dodekacdrii-.che or an irregular Kr ir; ta 1J shape, for example that of a sphere or plate.

The: silver halide parts can be between the interior and the surface area a different halide composition or a uniform halide

Have composition. The relatively light-insensitive emulsion can be contaminated with cadmium, lead, iridium or contain rhodium ions. The relatively light-insensitive emulsion may be a surface latent emulsion Be an image type or an emulsion of the intra-latent image type. An emulsion with veil nuclei can also be used can be used in the interior region of the particles.

The relatively light-insensitive emulsion can undergo conventional chemical sensitization, i.e. sulfur, Gold and reduction sensitization. However, chemical sensitization is preferred not applied. According to the invention, an emulsion that has not previously been sensitized (the so-called non-ripening emulsion) is preferably used for the relatively light-insensitive emulsion.

The relatively light-insensitive emulsion can contain a cyanine dye, merocyanine dye, complex cyanine

20 dye, complex merocyanine dye, holopolar

Cyanine dye, hemicyanine dye, styryl dye or contain hemioxonol dye. Furthermore, a desensitizing dye generally used in conventional negative emulsions are not used due to their strong desensitizing effect will. In addition, it can be relatively light-insensitive Emulsion contain an anti-fogging agent or a stabilizer. For example, an antifoggant or a stabilizer, such as an azole, a heterocyclic mercapto compound, thioketo compound, an azaindene, benzenethiosulfonic acid or benzenesulf in acid can be used.

According to the invention, the relatively light-insensitive emulsion layer can be a dye or a dispersion a sparingly soluble synthetic polymer.

The relatively light-insensitive emulsion layer can

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nt U m w μ

contain a coupler. A coupler is preferably in an amount of 0.3 mol or less, particularly 0.1 mol or less per mol of silver. Each of the yellow couplers, magenta couplers, cyan couplers, colored Couplers and DIR couplers as specifically below can be used. Likewise, compounds can be used when coupling with the oxidation product a developer providing a colorless compound can be used. Non-color-forming, competing compounds are preferred, particularly in terms of graininess in some cases. Furthermore, the use colored coupler may be preferred in some cases from the viewpoint of color reproducibility. About that in addition, the use of DIR couplers or DIR connections can be used from the point of view of graininess, sharpness, color reproducibility and / or gradation regulation may be preferred in some cases.

The silver halide photographic light-sensitive material having at least two light-sensitive silver halide emulsion layers, which according to the invention are sensitive to light of predominantly the same spectral range is a photographic, light-sensitive one Silver halide material with a blue sensitive layer and a green sensitive layer and / or a red-sensitive layer, each of these light-sensitive layers or all of these light-sensitive layers of at least two light-sensitive Layers are composed. A photographic, light-sensitive silver halide material with at least two blue-sensitive layers, at least two green-sensitive layers and at least two red-sensitive layers is particularly preferred.

Are there two or more groups of photosensitive Layers made up of at least two light-sensitive layers that are predominantly the same in relation to light Are sensitive to the spectral range, are composed,

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where erf indungsgernäßen, photographic light-sensitive material before, the relatively light-insensitive layer between at least one aer groups may be light-sensitive layers or the relatively light

5 insensitive layers can be between two or

several of the groups of photosensitive layers are present .

According to the invention, the silver halide emulsion layers are which are sensitive to light of predominantly the same spectral range, on or below the relative The non-sensitive layer is in direct contact with it.

The couplers can be used in the present invention for any kind of conventional color photographic silver halide photosensitive materials including, for example, color negative films, color papers, color positive films, slide color reversal films, color reversal films for cinematographic purposes and color reversal films for television purposes and the like. The couplers are particularly effective for color negative films or color reversal films which are required to have both high speeds and high image qualities.

With the recent sharp rise in the price of silver. which is a raw material for photographic photosensitive materials, the reduction in the amount of silver to be used in the photographic photosensitive materials has become extremely important, particularly in the case of X-ray films which require the use of large amounts of silver. From this viewpoint, the use of dyes in X-ray films 105247 was (see, for example, via the incorporation of a black color image riden coupler. For example, U.S. Patent No. 3,622,629, 3 73 ¹ J 735 and 4,126,461 or JA-OS 42725/77, / 80 and 105248/80) or a combination of couplers that form three different colors (see, for example, Research

ORIGINAL BATHROOM

Disclosure , No. 17123) proposed. The couplers according to the invention can be used with particular effectiveness in X-ray films, since they result in a much more effective use of silver and, at the same time, in a

5 contribute to faster processing.

The photographic emulsion layers of the photographic, light-sensitive materials according to the invention can contain, in addition to the couplers according to the invention, conventional color-forming couplers, ie compounds capable of forming color upon oxidative coupling with aromatic primary amine developers during the course of color development processing (for example phenylenediamine or Aminophenol derivatives) Examples of such couplers include magenta couplers such as 5-pyrazolone couplers, pyrazole benzimidazole couplers, cyanoacetyl coumarone couplers and open chain acylacetonitrile couplers; Yellow couplers such as acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides); and cyan couplers such as naphthol and phenol couplers. The use of couplers which contain a hydrophobic group (a so-called ballast group) within the molecule or of polymeric, non-diffusive couplers is preferred. These can be 2 or 3-equivalent couplers with respect to silver. It is also possible to use couplers, which are capable of forming a dye having a proper diffusibility in the development, such as those described in GB-OS PO83 b ^l \ 0 A. Further examples of useful couplers include colored couplers capable of providing color correction effects, couplers capable of releasing development inhibitors during the course of development (the so-called DIR couplers) and non-color forming DIR coupler compounds capable of releasing development inhibitors and colorless coupling products form.

In addition to these couplers, the photographic.

λΟ

C -f

55

non-color-forming photosensitive materials according to the invention Couplers which can form colorless coupling products, infrared couplers which lead to the formation of Dyes that absorb infrared rays during coupling, capable or black color-forming couplers which are capable of forming black color images upon coupling are able to contain.

Specific examples of usable according to the invention, purple color-forming couplers include those as described in U.S. Patents 2,600,788; 2,983,608; 3 062 653, 3 127 267, 3 311 476, 3 419 391, 3 519 429, 3 553 319, 3 582 322, 3 615 506, 3 834 908, 3 891 445, 3 926 631, 3 928 044, 4 076 533, 4 189 321 and 4 220 470, DE-PS 1 810 464, DE-QS 2 408 665, 2 417 945, 2 418 959,

2 424 467, 2 536 191, 2 651 363, 2 935 848 and 2 944 601, JA-PS 6031/65, 38498/79, 10901/80, 29420/80 and 29421/80 or JA-OS 74027/74, 129538/74, 60233/75, 159336/75, 20826/76, 26541/76, 105820/76, 42121/77, 58922/77,

20 9122/78, 48540/79, 80744/79, 62454/70 and 118034/80.

Specific examples of yellow color-forming couplers useful in the present invention include those as described are in U.S. Patents 2,875,057, 3,265,506, 3,408,194, 3,551,155, 3,582,322, 3,725,072, 3,891,445,

3 894 875, 3 973 968, 3 990 896, 4 008 086, 4 012 259,

4,022,620, 4,029,508, 4,046,575, 4,057,432, 4,059,447, 4,095,983, 4,133,958, 4,157,919, 4,182,919, 4,182,630, 4,186,019, 4 203 768 and 4 206 278 , DE-PS 1 547 868, DF-OS 2 213 461, 2 219 917, 2 261 36I, 2 263 875, ?. 414 006, 2 528 638, 2 935 849 and 2 936 842, GB-PS 1,425 020, JA-PS 12576/74, 10783/76, 36856/79 and 13023/80, JA-OS 26133/72, 66835/73 , 6341/75, 34232/75, 87650/75, 130442/75, 75521/76, 102636/76, 145319/76, 21827/76, 82424/77, 115219/77, 48541/79, 121126/79, 2300 / 80, 36900/80, 38576/80 and 7084i / 80 or Research Disclosure , No. 18053.

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Specific examples of cyan color forming couplers useful in the present invention include such as them are described in U.S. Patents 2,369,929, 2,434,272,

2 474 293, 2 521 908, 2 895 826, 3 034 892, 3 311 476, 3 458 315, 3 476 563, 3 583 971, 3 591 383, 3 758 308,

3 767 411, 4 004 929, 4 052 212, 4 124 396, 4 146 396 and 4 205 990, DE-OS 2 214 489, 2 414 830, 2 454 329,

2 634 694, 2 841 166, 2 934 769, 2 945 813 , 2 947 707 and 3 005 355, JA-PS 37822/79 and 37823/79 and JA-OS

10 5055/73, 59838/73, 130441/75, 26034/76, 146828/76, 69824/77, 90932/77 52423/78, 105226/78, 110530/78, 14736/79, 48237/79, 66129/79, 131931/79, 32071/80, 65956/80, 73050/80 or 108662/80.

Specific examples of colored couplers useful in the present invention include those described are in U.S. Patents 2,521,908, 3,034,892, and 3,476,560, DE-OS 2 4i8 959, JA-PS 22335/63, 11304/67, 2016/69 and 32461/69 or JA-OS 26034/76 and 42121 / 77-

Specific examples of those that can be used in the present invention DIR couplers include those as described U.S. Patents 3,227,554, 3,617,291, 3,632,345, 3,701,783,

3 790 384, 3 933 500, 3 938 996, 4 052 213, 4 157 916, 4 171 223, 4 183 752, 4 187 110 and 4 226 934, DE-OS 2 414 006, 2 454 301, 2 454 329 , 2 540 959, 2 707 489, 2 709 688, 2 730 824, 2 754 281, 2 835 073, 2 853 362, 2 855 697 and 2 902 681, GB-PS 953 454, JA-PS i6i4i / 76, 2776/78 and 34933/80, JA-OS 122335/74, 69624/77, 154631/77, 7232/78, 9116/78, 15136/78, 20324/78, 29717/78, 13533/78, 143223/78 , 73033/79, 114241/79, 115229/79, 145135/79, 84935/80 and 135835/80, or Researc h Disclosure, No. 181O4.

Further examples of usable couplers which are a development inhibitor release include those such as by the action of a timing group Release development inhibitors as described in

BATH ORIGINAL

5T 1 of GB-PS 2 010 818 B and GB-OS 2 07? 363 A.

The photographic, photosensitive Materials can be used to release development inhibitors during the course of development capable compounds other than DIR couplers, contain. Examples of compounds that can be used include those described in US Pat. Nos. 3,297 W and 3,379,529, DE-OS

2,417,914 or JA-OS 15271/77 and 9116/78. 10

Specific examples of non-color forming agents which can be used in the present invention Couplers include those described in U.S. Patents 3,912 and 4,204,867 or JA-OS 152721/77.

Specific examples of infrared couplers useful in the present invention include those described in U.S. Patent 4,178,183, JA-OS 129036/78, or Research Disclosure , Nos. 13460 and 18732.

Specific examples of usable black color formers Couplers include those described in U.S. Patents 4,126,461; 4,137,080 and 4,200,466 or JA-OS 46029/78, 133432/78, 105247/80 and 105248/80.

The emulsion layers of the photographic, light-sensitive materials can be a polymeric in combination with the coupler of the present invention Coupler included. Specific examples of polymeric couplers that can be used include those as described in U.S. Pat U.S. Patents 2,698,797, 2,759,816, 2,852,381, 3,163,652,

3 208 977, 3 211 552, 3 299 013, 3 370 952, 3 ^ 24 583,

3 451 820, 3 515 557, 3 767 412, 3 912 513, 3 926 436,

4,080,211, 4,128,427 and 4,215,195 or Research Disclosure , nos. 17825, 18815 and 19033.

The couplers of the invention can be prepared using known methods including those such as described in US-PS 2,322,027, in SiI-

BADORIGINAU

Overhalide emulsion layers are incorporated.

For example, the couplers can be dissolved in a solvent and then dispersed in a hydrophilic colloid. Examples of such solvents which can be used for this process include organic solvents having a high boiling point, such as alkyl esters of phthalic acid (e.g. dibutyl phthalate, dioctyl phthalate or dicyclohexy phthalate), phosphates (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl hexyl phosphate, trioctyl phosphate, or trioctyl phosphate hexyl phosphate, trioctyl phosphate hexyl phosphate, trioctyl phosphate hexyl phosphate, trioctyl phosphate hexyl phosphate, trioctyl phosphate hexyl phosphate, trioctyl phosphate hexylphosphate) Tributyl acetyl citrate), benzoates (for example octyl benzoate), alkylamides (for example diethyl lauryl amides), esters of fatty acids (for example dibutoxyethyl succinate or dioctyl acetate) and trimesates (for example tributyl trimesate); and organic solvents with a boiling point of about 30 to about 150 ° C., such as lower alkyl acetates (eg ethyl acetate or butyl acetate), ethyl propionate, sec-butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate or methyl cellosolve acetate. If desired, mixtures of the above-described high-boiling point organic solvents and the above-described low-boiling point organic solvents can also be used.

It is also possible to use the dispersing process described in JA-PS 39853/76 and JA-OS 599 ^ 3/76 Use of polymers to apply.

Of the compounds of the invention, those with an acid group, such as a carboxy or sulfo group, be introduced into hydrophilic colloids as an aqueous, alkaline solution.

The photograph] see ejmusionsschiehten and other layers in the photographic, light-sensitive materials ^ emciP. of the invention are au / ¹ flexible support, such as "-. y nt he ti see resin films, paper, or tissue, or on rigid support such as glass, ceramic or metal, which

410616

conventionally used for photographic light-sensitive materials. Examples of suitable carriers include flexible films composed of semisynthetic or synthetic high molecular weight material] ien, such as cellulose nitrate, cellulose acetate, Cell u] oseacetatbuty ra t, polystyrene, polyvinyl chloride, Po lyethy] ο nt. ^ repbthal at or polycarbonate as well as paper that is coated or laminated with barite or od-Qlefinpolymeren (for example polyethylene, polypropylene or ethylene / butene copolymer). The supports can be colored with dyes or pigments. They can be black in color for light shielding purposes. The surface of these supports is generally subjected to an underground treatment in order to improve the adhesion to the photographic emulsion layer and the like. The surface of the carrier can be subjected to a corona discharge, a treatment with UV light or a flame treatment, before or after the underground treatment.

During the preparation of the emulsions, a removal soluble salts are run from the emulsions after the formation of precipitates or physical ripening, using the pasta washing method, at deir; Gelatin is gelled, or a flocculation process using inorganic salts, anionic surface-active Agents, anionic polymers (for example polystyrene sulfonic acid) or gelatin derivatives (e.g. acylated gelatin or carbamoylated

30 gelatin).

The silver halide emulsions are usually used chemically sensitized. Applicable chemical sensitization methods are procedures as described in H. Frieser, The Basics of Photographic Processes with silver halides (Academic Publishing Company, 1968), pages 675 bis

BAD ORIG5NAL

It can be used individually or in combination ^a sulfur sensitization method using active gelatin and sulfur-containing compounds that are capable of reacting with silver (e.g., thiosulfates, thioureas, mercapto compounds or rhodanines), comprises a reduction sensitization method which comprises Use of reducing substances (e.g. tin (II) salts, amines, hydrazine derivatives, formamidinesulfinic acid and silane compounds) includes and a noble metal sensitization method that includes the use of noble metal compounds (e.g. gold complex salts and complex salts of metals from Group VIII of the periodic table, such as such as Pt, Ir or Pd).

Examples of suitable sulfur sensitization methods are described in U.S. Patents 1,574,944, 2,410,689, 2,278,947, 2,728,668, and 3,656,955, from reduction sensitization procedures in U.S. Patents 2,983,609, 2,419,974 and 4,054,458 and precious metal sensitization methods in U.S. Patents 2,399,083 and 2,448,060 or British Patent 618,061.

As a binder or protective colloid for the photographisehen Emulsions of the photographic light-sensitive materials of the present invention are used advantageously Gelatin is used, but other hydrophilic colloids can also be used.

The use of proteins as efwa Geia 1 1 nederi va to, graft is possible, for example oku of gelatin and other hoohmoJ.] Arfiewi ent strength materials, albumin, Cnaein and calibrate üerp-J, saccharides such as cellulose derivatives such as HydroxyethyicelIuI eyelet, Carboxymethyl cellulose or cellulose sulfate, sodium alginate, starch dorjvaten and the like as well as various syntheti.chen. hydrophil on, high molecular weight substances, such as homopolymers or copolymers, for example polyvinyl

fr

alcohol, polyvinyl alcohol half-acetal, poly-N-vinylpyrrolidone, Polyacrylic acid, polymethacrylic acid, polyacrylamide, Polyvinyl imidazole or polyvinyl pyrazole.

As gelatin, not only lime-treated gelatin but also acid-treated gelatin and enzyme-treated gelatin can be used, as described in Bull. So c. May be. Phot. Japan , No. 16, p. 30 (1966). Furthermore, hydrolyzed products or enzymatic products of gelatin can also be used.

Furthermore, dispersions of water-insoluble or sparingly soluble synthetic polymers may be present in the photographic emulsion layers and other hydrophilic colloid layers of the photographic light-sensitive materials of the present invention in order to improve the dimensional stability. For example, it is possible to use polymers which are composed of one or more monomers selected from alkyl acrylates, alkyl methacrylates, alkoxyalkyl acrylates, alkoxyalkyl methacrylates, glycidyl acrylates, glycidyl methacrylates, acrylamide, methacrylamide, vinyl esters (e.g. vinyl acetate ) , acrylonitrile, olefins, Styrene and polymers which are composed of a combination of the monomers described above and acrylic acid, methacrylic acid, etc. , ^ -unsaturated dicarboxylic acid, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, sulfoalkyl acrylate, sulfoalkyl methacrylate or styrene sulfonic acid.

The hydrophilic colloid layers in the photographic light-sensitive materials according to the invention, if they contain dyes or UV absorbers, can be stained using cationic polymers. For example, polymers as described in GB-PS ¹ 685 J ⁷ S, U.S. Patent No. 2,675,316, 2,839,401, 2 88? 156, 3 048 487, DE-OS 1 914 362 or JA-OS 47624/75 and 71332/75 can be used. _BATH ORIGINAL,

■ 62

The photographic emulsion layers and other hydrophilic colloid layers of the photographic light-sensitive materials of the present invention can contain inorganic or organic hardeners. For example, chromium salts (chrome alum or chromium acetate), aldehydes (formaldehyde, glyoxal or glutaraldehyde), N-methylol compounds (dimethylolurea or methylol dimethylhydantoin), dioxane derivatives ( 2,3-dihydroxydioxane), active vinyl compounds can be used alone or in combination (1,3,5-triacryloylhexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol or 1,2-di (vinyl-sulfonylacetamide) ethane), active halogen compounds (2,4-dichloro-6-hydroxy -s-triazine) and mucohalogenic acids (mucochloric acid or mucophenoxychloric acid).

The photographic emulsion layers and other hydrophilic koiloid layers in the photographic, Photosensitive materials can use surfactants for various purposes, for example as a coating aid or to prevent electrical charging, improve the Slip properties, emulsification, adhesion prevention, improvement of photographic properties (for example Development acceleration, high gradation

25 or sensitization).

For example, nonionic, surface active agents, such as saponin (steroid), Alky 1enoxide derivatives (e.g. polyethylene glycol, polyethylene glycol / F'olypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters. Polyethylene glycol sorbitan esters, polyethylene glycol alkylamines or amides or polyethylene oxide adducts from silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides and alkylphenol polyglycerides),

Esters of polyhydric alcohols with aliphatic acids or i d-alkyl ester; anionic surface-active agents

te], containing acid groups, such as a carboxy, SuI f o,, * -

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Phospho, sulfate or phosphate group, such as alkyl carboxylic acid salts , Alkyl sulfonic acid salts, alkylbenzene sulfonic acid salts, Alkyl naphthalenesulfonic acid salts, alkyl sulfuric acid esters, Alkyl phosphoric acid esters, N-acyl-N-alkyltaurines, sulfosuccinic acid esters, suIfoalkyl-polyoxyethylene alkylphenyl ethers or polyoxyethylene alkyl phosphoric acid esters ; amphoteric surfactants such as for example amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfonic acid esters or phosphoric acid esters, alkyl betaines or amine oxides; and cationic surfactants Agents, such as alkyiamine salts, aliphatic or aromatic, quaternary ammonium salts, heterocyclic, quaternary ammonium salts, such as pyridinium salts, imidazolium salts, alphatic or heterocyclic sulfonium salts, aliphatic or heterocyclic phosphonium salts In addition, fluorine-containing surfactants can be used.

The photographic emulsion layers of the invention, photographic light-sensitive materials can be any of silver bromide, Silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride. A preferred silver halide is silver iodobromide.

The photographic emulsions used in the present invention can be spectrally sensitized by methine dyes and others will. Although these sensitizing dyes can be used alone, if desired, a combination of two or more of these is used. A combination of sensitizing dyes is often used for super-awareness purposes. The emulsions can contain dyes, which themselves do not have a spectral sensitization function or substances which do not significantly affect visible light absorb and super-sensitize along with the sensitizing dyes.

BATH ORIGINAL

Suitable Γ, -. -Sibilizing dyes, combinations of color ¹ "" -. 'Η which show super-sensitization and substance ·., -Ie show super- "sensitization, are in Research iisclosure , Vol. 176, No. 17643, p 23, IV-J

5 (December 1978).

The hydrophilic colloid layers in the inventive, Photographic light-sensitive materials can use water-soluble dyes as filter dyes or for the purpose of preventing radiation or for other purposes. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl Dyes, merocyanine dyes, and cyanine dyes Azo dyes. Oxonol-, hemi-

15 oxonol and merocyanine dyes.

For the purpose of increasing sensitivity, increasing contrast or development acceleration, the photographic emulsion layers of the invention, photographic light-sensitive materials, for example polyalkylene oxide or derivatives thereof, such as for example ethers, esters or amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, urethane Derivatives, urea derivatives, imidazole derivatives or 3-pyrazolidones contain. For example, it is possible to use the US Pat. No. 2,400,532, 2,423,549, 2,716,062, 3 617 280, 3 772 021 and 3 808 003 or GB-PS 1 488 991.

The photographic emulsions used according to the invention Numerous compounds can also be used for the purpose of preventing fogging or for the purpose of stabilization the photographic properties during the manufacture of the photographic, photosensitive Materials, during their storage or during the photographic processing included. Deployed For example, numerous known antifoggants can be used oiii-r stabilizers such as azoles, e.g.

^BAD or, g, _nal

Benzothiazolium salts, metroindazoles, triazoles, benzotriazoles or benzimidazoles (especially nitro or halogenated substitutes Benzimidazoles); heterocyclic mercapto compounds, e.g. mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazole, mercaptothiadiazole, mercaptotetrazoie- (especially i-phenyl-5-mercapto-tetrazoi) or mercaptopyrimidines; the above, heterocyclic Mercapto compounds having water-soluble groups such as a carboxy or sulfo group; Thioketo compounds, e.g., oxazolinethione; Azaindenes, e.g.

Tetraazaindenes (especially 4-hydroxy- (1,3,3a, 7) -tetraazaindenes); Benzoithiosulfonic acids; Benzenesulfinic acids.

The photographic, light-sensitive according to the invention Materials can be used as color haze-preventing agents hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, Contain ascorbic acid derivatives.

In the context of the present invention, known.

anti-fading agents can be used.

Color image stabilizers can also be used if they are in the Can be used within the scope of the invention, used alone or as a mixture of two or more of these. Examples of well-known anti-fading agents

25 include hydroquinone derivatives, gallic acid derivatives,

p-alkoxyphenols, p-oxyphenol derivatives or bisphenols.

Specific examples of hydroquinone derivatives are described in US Patent No. 2,360,290, 2 418 6 ¹ 3. 2 675 31 ^. 2 701 197, 2 704 713, 2 728 659, 2 732 300, 2 735 765,

2,710,801 and 2,816,028 or GB-PS 1,363,921, of gallic acid derivatives in US-PS 3,457,079 and 3,069,268, of p-alkoxyphenols in US-PS 2,735,765 and 3,696,909 or JA-PS 20977/74 and 6623/77, of p-Qxyphenol derivatives in U.S. Patents 3 ^ 32,300, 3,573,050, 3,574,627 and

3 764 337, JA-OS 33633/77, 147434/77 and 152225/77 and of bisphenols in U.S. Patent 3,700,455.

.- ^, copy

BATH ORIGINAL

The emulsion layers or adjacent layers thereof in the photographic, photosensitive ones according to the invention For the purpose of image stabilization, materials can contain UV absorbing agents, as described in

5, U.S. Patents 3,250,617 and 3,253,921.

The present invention can be used for photographic light-sensitive materials having a low silver content can be applied, the amount of silver halide in the emulsions being one-half to one-hundredth that of conventional, photographic, light-sensitive Materials is. In such color photographic light-sensitive materials with low Silver halide content, satisfactory color images can be obtained by an image forming method, in which the amount of colorants formed by applying color enhancement using peroxides, Cobalt complex salts or sodium chloride (see for example DE-OS 2,357,694, US-PS 3,674,490 and 3,761 265, DE-OS 2 044 833, 2056 359, 2 056 360 and 2 226 770 or JA-OS 9728/73 and 9 729/73) is increased.

Color development of the photographic light-sensitive materials of the present invention can be performed using conventional procedures'.

That is, a negative-positive method comprising performing color development can be used with a substituted p-phenylenediamine to form a? Color and a silver picture, the processing using a bleach bath to oxidize the silver image into a silver salt and remove the rest Silberhaiogenj ds and other silver salts by dissolving taking · Verwonoung a fixer to the color image and a color reversal process comprising forming a negative. Silver image through development with a developer solution containing a black-and-white developer, carrying out at least one uniform Exposure or suitable alloy

^ß AD ORIGINAL

yt ^r3

treatment, and finally carrying out color development, bleaching and fixing to make a positive Get color image.

It is also used in color X-ray films one developed silver image and one developed Color image possible to apply a method that the Includes color development and fixing, but does not include bleaching.

The temperature in these color photographic processings generally ranges from about 18 to about 50 ° C, but a temperature below 18 ° C can also be used or above 50 ° C.

Many known p-phenylenediamine derivatives can be used for developing the photographic light-sensitive materials of the present invention. A special one? suitable type of p-phenylenediamine color developer includes Ν, Ν-dialkyl-p-phenylenediamine compounds, the alkyl and phenyl groups of which may be substituted. Examples of particularly suitable compounds include N, N-Di e thy lp-phenylenedianjin-hy arochloride, N-methyl-p-phenylenediamine hydrochloride, Ν, Ν-dimethyl-p-phenylenediamine hydrochloride, 2-araino-5- (N-ethyl -N-dod ^ cylarninojtoluene. N-Ethyi-N- (p-methane-sulfonamidoethyl-S-methyl - ^ - aminoaniline sulfate, N-ethyl-N-ρ-hycroxyethylaminoaniline, ^L -Arcino-N- (2-methoxyethyl) - N-ethyl-3-raethy! Aniline-p-toluenesulfonate ,. N, N-diethyl-3-methyl - ^ - arninoarii 1 in or N-ethyl-W-

30 (ρ -hydroxyethyl; -3-ethy l - ^ - amin.-.- ani 1 in.

In addition, the compounds as described in L.F.A. Mason, Photographic Processing Chemistry (Focal Press, 1966). Pages 226 to 22 ^. U.S. PS

35 2 193 015 and 2 592 36 ^ or JA-OS 64933/73.

The color developing solution may contain pH buffers, development restrainers, or antifoggants. If e

the developer solution can contain water softeners, preservatives, organic solvents, development accelerators, dye-forming couplers, competing couplers, fogging agents, auxiliary developing agents, Contain thickeners, polycarboxylic acid gellants, or antioxidants.

The bleaching processing can be carried out simultaneously with the fixing processing or these processings can be carried out separately. Suitable bleaching agents include Compounds of polyvalent metals, such as iron (III), cobalt (III), chromium (VI) or copper (II),

* Peracids, quinones or nitroso compounds. Example

wise can be used ferricyanide, bichromate,

■ 15 organic complex salts of iron (III) or cobalt (III), j complex salts of aminopolycarboxylic acids, such as ethylene

diamine tetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanol tetraacetic acid and the like or organic acids such as citric acid, tartaric acid or maleic acid; Persulfates, permanganates or nitrosophenol.

Among these, potassium ferricyanide, sodium (ethylenediaminetetraacetato) iron (III) and ammonium (ethylenediaminetetraacetato) iron (III) are particularly preferred. The (ethylenediaminetetraacetato) iron (III) complex salts are suitable for both the bleaching solution and the bleach-fixing solution in the form of a single bath.

In the bleach solution or bleach-fix solution, numerous Additives are present including bleach accelerators as described in U.S. Patents 3,042,520 and US Pat 3 2 ^ 1 966, JA-PS 8506/70 and 8836/70, thiol compounds, as described in JA-OS 65732/78.

Examples of suitable fixing agents include 35 "thiosulfates (e.g., ammonium thiosulfate, sodium thiosulfate, or potassium thiosulfate.) , Thiocyanides (e.g. ammonium thiocyanide, sodium thiocyanide or potassium thiocyanide) and thioether compounds, such as 3,6-dithia-1,8-octanediol. These

BAD ORJGfNAL

Compounds can be used alone or as a mixture of two or more of these can be used.

The following examples illustrate the invention. Unless otherwise stated, all refer to Parts, percentages, ratios and the like by weight.

example 1

Layers of the compositions shown below were coated on a cellulose triacetate film support, uis a color photographic, photosensitive

to produce r- multilayer material. ι ο

1st layer : Antihalation layer Gelatin layer containing black, colloidal silver

2nd layer : intermediate layer.

Gelatin layer, containing a dispersion of 2, 5-di-tert-octylhydroquinone

3rd layer: First red-sensitive emulsion layer

Silver iodobromide emulsion (iodide content 5 mol%),

amount of silver coated 1.6 g / m ^?

Sensitizing Dye I Sensitizing Dye II Coupler EX-I Coupler EX-2 Coupler EX-3

4th layer : Second red-sensitive emulsion layer, silver iodobromide emulsion (iodide content 7 mol%), amount of silver coated 1. U g / m ²

Sensitizing Dye I 3 χ ίο "- ³ moles per mole of silver

Sensitizing Dye II 1.2 10 mol per mol of silver

Coupler EX-4 0.0? Mo] per mole of silver

Coupler EX-2 0.0016 mole per cent mole silver

6 χ 10 " MoI Per Mole silver 1.5 x ΙΟ " ⁵ MoI Per Mole silver 0, OiJ MoI Per Mole Silver- 0.003 MoI Per Mole silver 0.0006 MoI Per Mole silver

BAD ORIGINA

1 5th layer: intermediate layer Same as second layer

6th layer : First green-sensitive emulsion layer
g silver iodobromide emulsion (iodide content 4 mol%),

coated amount of silver 1.2 g / m ²
Sensitizing Dye III 3 x 10 moles per mole of silver Sensitizing Dye IV 1 10 moles per mole of silver Coupler EX-5 0.05 moles per mole of silver

Coupler EX-6 0.008 moles per mole of silver

Coupler EX-3 0.0015 moles per mole of silver

7th layer: Second green-sensitive emulsion layer Silver iodobromide emulsion (iodide content 8 mol%),

amount of silver coated 1.3 g / m ²

Sensitizing Dye III 2.5 x 10 " ⁵ moles per mole of silver Sensitizing Dye IV 0.8 10 moles per mole of silver Coupler EX-7 0.017 moles per mole of silver

Coupler EX-6 0.003 moles per mole of silver

20 8th layer : yellow filter layer

Gelatin layer containing yellow, colloidal silver and a dispersion of 2,5-QL-tert-octylhydroquinone

9- Layer : First blue-sensitive emulsion layer
»Γ silver iodobromide emulsion (iodide content 6 mol%),

amount of silver coated 0.7 g / m ²

Coupler Ex-8 0.25 moles per mole of silver

Coupler Ex-3 0.015 moles per mole of silver

10th layer : Second blue-sensitive emulsion layer
^ύν S:] beriodobromide emulsion (iodide content 6 mol%),

coated amount of silver 0.6 g / m ²

Coupler EX-9. 0.06 moles per mole of silver

11th layer .: First protective layer

35 gelatin substance, containing silver iodobromide (Iodide content 1 mol%,

average particle size 0.07 µm) BAD OTIQSNAL aufbp. 'Coated silver amount 0.5 g / m ²

1 and a dispersion of the UV absorbing agents

EX-IO and EX-11

12th layer : Second protective layer _ gelatin layer, containing Polyraethylmnethacrylat-

Particles (about 1.5 µm in diameter) and formaldehyde scavenger EX-12

In addition to the above-described ingredients, gelatin hardener EX-13 and a surface active agent were used incorporated into each of the layers. The sample thus prepared was named Sample 101.

Light-insensitive emulsion layer 15th

In a reaction vessel, an aqueous silver nitrate solution and an aqueous potassium bromide solution were simultaneously added to an aqueous gelatin solution kept at 50 ° C while maintaining the pAg at 7.9 to form a silver bromide emulsion containing cubic silver bromide particles having a particle diameter of 0.1 * 1 μm to manufacture.

The above-described silver bromide emulsion was coated between the 9th and 10th layers of Sample 101 so that the coated amount of the cubic silver bronze was 0.25 g / m ² or 0.50 g / m ² , as shown in Table 1 below, to prepare a non-photosensitive emulsion layer.

Addition of the compound according to the present invention r.u. the 10th shift

The 10th layer was prepared in the same way as described above for the 10th layer of the sample 101, with the exception that each of the compounds (1), (8), (17), (21) and (32) was added in an amount shown in Table 1 below. Thus, samples 102 to 11 * 4 with the additions shown in the table below were

iAD ORIGINAL

1 compositions made.

Samples 101 to 114 thus produced lasted 16 hours exposed to conditions of 40 ° C and 70% humidity and then exposed to white light through a sensitometric test wedge and that described below Subjected to color development processing. The densities of the samples so processed were made using measured with a blue filter, and the sensitivities of these samples. The sensitivities obtained are shown in Table 1 below as reciprocal values the amount of exposure required to obtain an optical fog density of + 0.2. The sensitivity sample 101 was assumed to be 100 and the other sensitivities reported relative thereto.

In order to further determine the graininess of these samples, these were exposed in stages, the one shown below It was subjected to development processing and then the RMS values of these samples using a blue filter determined with an opening size of 48 μm. the RMS values thus obtained are multiplied by 1,000 and are shown in Table 1 below. The color development processing was at 38 ° C on the following

25 ways executed:

1. Color development 3 minutes and 15 seconds

?. R] calibrate 6 minutes and 30 seconds

"-;. Wash with water 3 minutes and 15 seconds'

H. Freeze 6 minutes and 30 seconds

',. Wash with water for 3 minutes and 15 seconds. 6. St a t'i for 1 minute and 15 seconds

The compositions of those used in each stage Processing solutions were as follows: 35

34106

color developer solution

Sodium nitrilotriacetate Sodium sulift

Sodium carbonate 5

Potassium bromide hydroxylamine sulfate 1- (N-ethyl-N- β- hydroxyethylamino) -2-methylaniline sulfate

Water on

Bleach solution

Ammonium bromide ammonia (28% aqueous solution)

Sodium (ethylenediaminetetraacetato) iron Glacial water on

1.0 £ H, 0 G 30.0 G ι, " G 2.4 G G 1 liter

160.0 g? 5.0 ml

130.0 g

liter

Fixing solution

Sodium tetrapolyphosphate Sodium sulfite ammonium thiosulfate (70% aqueous solution) sodium bisulfite Water on

Stabilization solution

Formaldehyde water to 2.0 g 4.0 g 175.0 ml 4.6 g 1 liter

8.0 ml

1 liter

BATH ORIGINAL

tab

101 102 103 10U 105 106 107 108 109 110 11 1 112 113 114

sample

(Control ■

(Comparison) (comparison) (according to the invention) (according to the invention) (Comparison) (according to the invention) (comparison) (according to the invention) (Comparison) (according to the invention) (Comparison) (according to the invention)

1 ichtuneir.pf young people
Emu1si onsschi cht link (g / m ² ) no 0.25 - 0.50 - no (21) 0.25 (21) 0.50 (21) no ( 8th) 0.50 ( 8th) no (D 0.50 (D no (32) 0.50 (32) no (17) 0.50 (17)

Amount of relative

added

link

1.2 χ 10 1.2 χ 1.2 χ 0.6 χ 10

0.6 χ 1i 0.03 0.03

2.4 χ 10 2.4 χ 4.8 χ 4.8 χ 10

-4

-4

-4

-4

Sensation
opportunity Grainy
speed 100 33 138 31 152 31 132 36 155 29 170 28 129 38 167 30th 125 37 158 30th 132 35 162 29 129 36 155 29

Moles of compound added per mole of silver halide in the tenth layer

CD CTJ

From the results shown in Table 1 it can be seen that the samples according to the invention 105, 106, 108, 110, and 114 apparently increased sensitivity have, "lsi comparison with the comparative samples 102 and 103, in which only the non-photosensitive emulsion layer is used and obviously with regard to the granularity are improved compared to the comparative samples 104, 107 ,. 109, 111 and 113, which only the compound according to the invention is added. It is also apparent that the invention Samples exhibited both increased sensitivity and improved graininess when compared to the control sample 101. It can thus be seen that the practice of the present invention is extremely effective.

15th

Example 2

Sample 115 was prepared in the same manner as described for sample from Example 1, with the exception.

² ^ that the silver halide emulsion of the 7th layer was replaced by a silver halide emulsion containing tabular grains with an average aspect ratio of 10 or more and an average thickness of 0.21 μm, as in Research Disclosure ,

Volume 225, No. 22534 (1983), contained the amounts of sensitizing dyes III and IV were increased to three times that in Example 1, and that furthermore the compound (24) according to the invention in one

Amount of 2.0 10 ~ moles per mole of silver was added. 30th

Sample 115 was subjected to the same processing and evaluation, as described in Example 1, subjected. As a result, it was confirmed that the sample 115 to which applied to the present invention exhibited increased sensitivity and improved granularity.

BAD ORIGINAL _C OPY ~

1 example 3

Sample 116 was made in the same manner as for Sample in Example 1, except that the coupler EX-9 of the 11th layer was replaced by the coupler EX-1 ^ replaces and continues to be the storage stabilizer EX-15 was added in an amount 0.005 mole per mole of silver.

Sample 116 was subjected to the same processing and evaluation as described in Example 1. as The result has been shown that the sample 116 to which the present invention had increased sensitivity and improved graininess.

The compounds used to prepare the above samples were as follows:

Sensitizing Dye I :

Pyridiniura salt of anhydro-5,5'-dichloro-3,3'-di (γ-sulfopropyl) -Q-ethylthiacarbocyanine hydroxide

Sensitizing Dye II :

Triethylamine salt of anhydro-9-ethyl-3,3'-di (y -sulfo-

propyl ) -k , 5,4 ', 5'-dibenzothiacarbocyanine hydroxide 25

3 sensitization dye III :

NatriufficaJi of anhydro-9-ethyl-5,5'-dichloro-3,3'-di (γ- sulfopropyl) oxacarbocyanine

Sensitization dye IV :

Sodium salt of anhydro-5,6,5 ', 6 · -tetrachloro-1,1'-diethyl-3. 3 '-di Γ (3 -j µ- (γ-sulfopropoxy) ethoxy ethyl I imidazoiocarbocyanine hydroxide
35

copy

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BATH ORIGINAL

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(π) C ₄ H ₉ CONH

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COOC ₁₂ H ₂ ,

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Claims (28)

25 30 35 Silver halide photographic light-sensitive material characterized by a
Support with at least two photosensitive silver halide emulsion layers located thereon, which are sensitive to light of predominantly the same spectral range, and one that is relatively light-insensitive, silver halide, zinc oxide or titanium oxide
containing layer, which is arranged between the two photosensitive silver halide emulsion layers, wherein at least one of the two photosensitive silver halide emulsion layers contains a compound of the following general formula (I): (I) COPY where mean: A is a residue of a compound necessary for coupling with the oxidation product of an aromatic, primary Amine developer by removing a hydrogen atom from the active position of the connection is able to u η d 3 a group which is released upon coupling and which has a concealing function in a developing solution. 2. Silver halide photographic light-sensitive material according to claim 1, characterized in that the remainder represented by A .c a residue of a cyan coupler, purple coupler, Yellow coupler or a non-color-forming coupler that is formed by the removal of a hydrogen atom is formed from their active position. 3- photographic light-sensitive silver halide material according to claim 1, characterized in that the group represented by B, _v fogging function-containing group is a group having a partial structure of a reducing compound 2g or a compound capable of forming silver sulfide, contains. 4. Photographic, light-sensitive silver halide Material according to claim 1, characterized in that g e k e η η OQ indicates that the compound represented by the general formula (I) is a compound of the following general formula (II) is: A- (TIME) _n -FA (II) where mean: A has the same meaning as given for A in the general formula (I) according to claim 1; copy BATH ORIGINARY TIME a tiring group that was released upon clutch becomes and then FA in <1er intw iekler In ^ un releases; η O c: ^ r ': FA a group which is releasable by coupling from A when η is 0 or is releasable from ΤΙΜΞ when η is 1 and can be adsorbed on silicon halide particles and has a concealing function predominantly with respect to silver halide. 5. The silver halide photographic light-sensitive material as claimed in claim h, characterized in that FA is a group of the following 2g formula represents: [AO- (L) -X- ra where mean: 2Q AD a group which adsorbs on silver halide particles can be; L is a divalent linking group; X is a reducing group or a group capable of forming silver sulfide during development; and in 0 or 1. 6. Photographic light-sensitive silver halide Material according to claim 4, characterized in that FA represents a group which can be adsorbed and reduced on silver halide or to form silver sulfide is capable of developing. 7- silver halide photographic3 light-sensitive material according to claim 4, characterized in that the R represented by A a residue of a cyan coupler selected from the group consisting of a residue of a phenol coupler and a .naphthoi coupler. 8. Silver halide photographic light sensitive material according to claim 4, characterized in that the remainder represented by A a residue of a purple coupler selected from the group consisting of a residue of a 5-pyrazolone coupler, Pyrazole benzimidazole coupler, pyrazole triazole coupler, Cyanoacetylcoumarone coupler, an open-chain acylacetonitrile coupler and an indazolone coupler. 9- Silver halide photographic light-sensitive material according to claim 4, characterized in that the remainder represented by A a residue of a yellow coupler selected from the group consisting of a residue of a benzoylacetanilide coupler, Pivaloylacetanilide coupler and malondianilide coupler. 10. Silver halide photographic photosensitive material according to claim 4, characterized in that the remainder represented by A a residue of a non-color forming coupler selected from the group consisting of a residue of an indanone, Cyclopentanons, a diester of malonic acid, an imidazolinone, an oxazolinone and a thiazolinone, is. 11. Silver halide photographic photosensitive material according to claim 4, characterized in that the remainder represented by A one by the following general formulas (III), (IV), (V), (VI), (VII), (VIII), (IX), (X) or (XI) the remainder shown is: ORIGINAL (I Γ Γ) in which mean. R- an acylamide, aniline or ureide group; and Rp is a phenyl group represented by one or more Substituents selected from the group consisting of halogen atom, alkyl group, alkoxy group and cyano group can be; (IV) (V) OH -R, 5 (VI) where mean: R ^ a halogen atom, an acylamide group or aliphatic Group; BATH ORIGINAL R ₁ . and R _n . in each case an aliphatic, aromatic or heterocyclic group, where one of R ₁ and R ₁ - can represent a hydrogen atom; a is an integer from 1 to 4; b 0 or an integer from 1 to 3; c 0 or an integer from 1 to 5; ίο, _{/ 7} R ₆ -C-CHCNH - // ⁰ ° ^R 7 '(VII) (^ XVnhcchcnh - // a> ^K 7 ^R 7 (VIII) where mean: Rg is a tertiary alkyl group or an aromatic group Group; R “is hydrogen atom, halogen atom or an alkoxy group; and an acylamide group, an aliphatic group, a coxycarbonyl, sulfamoyl, carbamoyl, Alk is a halogen atom or a sulfonamide group; Alkoxycarbonyl, sulfamoyl, carbamoyl, alkoxy group, (IX) where mean: Rq is an aliphatic group, an alkoxy, mercapto, Alkylthio, acyl amide, aikoxycarbony 1-, 3ulfonamide, Carba.T.oy i-. 3ul farnoy 1-, Alkoxysuifor.yl-, Aryl.oxysi.il-5 fonyl-, acyl-, diacylaraino-, alkylsulfony1- or aryl- sulfnyl group; and R _{10 represents} a hydrogen atom, halogen atom, an alkoxy, acyl, nitro, alkylsulfonyl or arylsulfonyl group; wherein the indanone group represented by the general formula (IX) is in the form of an Er.olester thereof may be present; 15 (χ; where mean: R _{11 is} an aliphatic or aromatic group; and V is an oxygen, sulfur or nitrogen atom; ^R 12 ~ ^C " ^R 13 H (XI) where mean: gg R.J2 ^and R-, τ each a group selected from the group of the following formulas -CNH ! I ² -CNHR ₁ , II ¹⁴ P. 14 -CN ^Lq Il ^ R ₁₅ , O ^ib 7 "' Il -SNHR,., Il ¹⁴ -SOR 14th , R, -SN ' 14th Ii -SNH Ii ² -CN, -CHO, '14 -NO 15 · 16 or -N W where mean: ^R ! 4 ', ^R 15 ^and R ₁₆ each represent a hydrogen atom, an aliphatic, aromatic or heterocyclic group; and copy 1 W those for the formation of a 5- or 6-membered ring together with the nitrogen atom, necessary non-metallic atoms or where R ₁ -, and R _1. , Lp. Grain ir.a t ion together with the necessary, non-metallic atoms 5 can form a 5- or 6-membered ring. 12. Photographic, light-sensitive Si i herha logeni> i material according to claim H, characterized in that - .; η η is characterized in that TIME is a group that is released in the coupling of A and then releases due to an intramolecular rearrangement reaction FA, a group FA release by electron transfer via a conjugated system or a group of a coupling component, which is able 15 is FA on coupling with the oxidation product to release an aromatic, primary amine developer . 13- Silver halide photographic photosensitive material according to claim 5, characterized in that the group represented by AD is a group formed by a nitrogen-containing, heterocyclic ring with a dissociable hydrogen atom, a heterocyclic containing at least one nitrogen atom and at least one other heteroatom Ring, a heterocyclic ring with a mercapto group, a quaternary salt, a thiophenol, an alkylthiol or a compound with the S.
Substructure ^ _c-, is derived. 14. A photographic, light-sensitive silver halide material according to claim 5, characterized in that the divalent connecting group represented by L is a member selected from the group consisting of alkylene group, alkenylene group, phenylene group, naphthylene group, -C-, -S-, -SO-, -SO ^ -, -N = N-, carbony 1 group, amide group, thioamide group, sulfonamide group, ureide group, thio- BAD ORtGINAU ureid group and heterocyclic group, is. 15. Silver halide photographic light sensitive material according to claim 5, characterized in that g e k e η η - δ shows that the X represented by reducing group is a group formed by a reducing compound selected from the group Hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine, 1-phenyl-3-pyrazolidinone., Enamine, aldehyde, polyamine, acetylene, aminoborane, quaternary salt and carbacic acid. 16. The silver halide photographic light-sensitive material according to claim 5, characterized in that the _t represented by X for forming silver sulfide upon development is a group which differs from a compound with the structure ^^ "" C- is derived and selected from a thiourea, thioamide, dithiocarbamate, Rhodanine, thiohydantoin and thiazolidinthione. 17. A photographic, photosensitive silver halide material according to claim U, characterized in that FA is bound to TIME or A at the point of its adsorption on the silver halide particles. 18. Photographic, light-sensitive silver halide-ο U Material according to claim 4, characterized in that FA is bonded to TIME or A at a position other than the site of its adsorption on the silver halide particles and the site _q of adsorption of FA is bonded to a hydrogen atom or to a group hydrolyzable or releasable in a developing solution is blocked. BAD ORJGlNAl 19- Silver halide photographic light sensitive material according to claim 1, characterized in that the amount of the general Formula (I) shown. Compound about 10 "moles to about 0.2 moles per mole of silver in the silver halide emulsion layer, which contains the compound represented by the general formula (I) . 20. Photographic, light-sensitive silver halide material according to claim 1, characterized in that the relatively light-insensitive Layer is a layer containing zinc oxide or titanium oxide. 21. Silver halide photographic light-sensitive material according to claim 20, characterized in that the particle size of the zinc oxide or titanium oxide is about 0.05 to about 0.8 μm. 22. Photographic, light-sensitive silver halide material according to claim 1, characterized in that the relatively light-insensitive Layer a relatively light-insensitive silver halide emulsion layer which contains predominantly light-insensitive silver halide. 23. Photographic, light-sensitive silver halide material according to claim 22, characterized in that g e k e η η draws, that the silver halide of the relatively light-insensitive silver halide emulsion layer 60 mol% or more of silver bromide, 30 mol% or less Contains silver chloride and 40 mol% or less of silver iodide. 24. Photographic, light-sensitive silver halide material according to claim 22, characterized in that the particle size of the silver BATH ORIGINAL 12 1 halide is about 0.6 µm or less. 25. Photographic, light-sensitive silver halide material according to claim 22, characterized in that g e k e η η, that the silver halide emulsion is a silver halide emulsion in which more than 90%, on a weight or number basis, of the total silver halide particles in the size range within + · 40% of the mean particle size are present. 10 26. Photographic, light-sensitive silver halide material according to claim 22, characterized in that the amount of the coated silver halide emulsion, based on silver, is 0.03 g / m ² 15 to 5 g / m ² . 27. Photographic, light-sensitive silver halide material according to claim 22, characterized in that the silver halide emulsion is a non-chemically sensitized silver halide emulsion. 28. Photographic, light-sensitive silver halide material according to claim 22, characterized in that g e k e η η, that the relatively light-insensitive silver halide emulsion layer also has one Contains coupler. 29- Silver halide photographic light-sensitive material according to claim 1, characterized in that the photographic material at least two blue-sensitive silver halide emulsion layers , at least two green-sensitive silver halide emulsion layers and at least two red-sensitive silver halide emulsion layers. copy ₍ IAD ORIGINAL